Process and apparatus for alkyl halide fumigant recovery and conversion

ABSTRACT

Process and apparatus (10) are disclosed for capturing and converting an ozone-depleting alkyl halide fumigant from a fumigant/air mixed stream (14) by absorbing it into a metal hydroxide-alcohol buffer solution (26) in an absorber/scrubber (12) to produce a fumigant-free air stream (28). The captured alkyl halide in aqueous alcohol solution can actively react with the metal hydroxide in alcohol solution to produce a value-added product, such as a precipitate metal halide, and another alcohol that further enhances absorption. The absorbing solution is well-mixed with make-up alcohol and alkali streams to maintain the concentration of the metal hydroxide in the desired buffer solution range. The solid precipitate metal halide (52) is separated from the liquid stream, and the metal hydroxide-containing mixed alcohol stream (26) is recycled to the absorber/scrubber (12).

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. patent application Ser. No.16/648,632, filed Mar. 18, 2021, now issued as U.S. Pat. No. 11,420,158,which is a national phase entry, under 35 U.S.C. § 371, of InternationalApplication No. PCT/U.S.2018/053219, filed Sep. 27, 2018 and entitled“PROCESS AND APPARATUS FOR ALKYL HALIDE FUMIGANT RECOVERY ANDCONVERSION”, which claims the benefit of and priority to U.S.Provisional Patent Application Ser. No. 62/563,976 filed Sep. 27, 2017,the contents of all of which are fully incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to cost-effective processes and apparatusfor the treatment of fumigation waste/exhaust gas, and, moreparticularly, to the recovery of alkyl halide from an air streamcontaining same and the concomitant conversion of the recovered alkylhalide into useful compounds.

BACKGROUND OF THE INVENTION

Fumigants are used to treat agricultural products, such as fruits,grains or logs, in enclosures before these products are allowed to beexported overseas, imported or distributed locally. After fumigation,sufficient time elapses for the fumigant to be absorbed by the products.Subsequently, the enclosures are aerated, causing the release ofresidual fumigant, which can be as high as 50% of the original amountapplied, into the atmosphere. Alkyl halides, especially methyl bromide(MeBr), are commonly used fumigants.

Due to its toxicity, methyl bromide is considered to be an effectivequarantine/phyto-sanitary fumigant in the control of insects and otherpests. However, studies in humans have confirmed acute and chronichealth effects associated with methyl bromide, and the EPA hasclassified methyl bromide as a Group D compound. In addition to itstoxicity, another serious concern about the use of methyl bromide is thedamage it causes to the stratospheric ozone layer. In fact, methylbromide is considered an ozone-depleting chemical and thus it has beenclassified as a Class I ozone-depleting substance by the Montrealprotocol, while also falling under the Clean Air Act with an ozonedepletion potential of 0.2%. As a result, international, federal andstate regulations require strict control of methyl bromide emissionsbecause of their hazardous effect on the environment.

Due to the lack of effective alternatives, the use of methyl bromide asa fumigant has not been completely discontinued, but such usage is onlypermitted if its emissions can be sufficiently reduced. This has anadverse economic impact on, for example, logging companies, which arelimited by federal and state regulations on how much of the fumigantthey can release into the atmosphere, thus limiting their operations.

Currently, there are methods being implemented on a large scale forcapturing fumigants; however, they typically destroy the fumigants,creating by-products and attendant disposal problems. Moreover, they arealso expensive. Most of the current methods rely on the use of activatedcarbon beds, and the absorbing solution is not recoverable. Othershortcomings associated with these current technologies include thefollowing, for example. They involve complicated systems comprisingmultiple stages, thus requiring high capital investment and operatingexpense. These technologies often require the modification of existingfumigation processes which may affect the effectiveness and reliabilityof the processes by, for example, requiring longer processing time percontainer. The existing emission control methods/processes mainly focuson the capture of the halogenated fumigants using differentadsorbents/absorbents, whereby a further treatment process is usuallyrequired for the safe disposal of the halogen-containingagents/absorbents, which adds extra costs to the process and makes itless economically favorable. Current treatment systems are typicallylarge which makes their transportation for onsite gas treatmentdifficult. Existing processes also typically involve extreme treatmentconditions of high temperature or energy input.

SUMMARY OF THE INVENTION

The present invention relates to processes and apparatus for capturingand converting fumigants using a reactive absorber/scrubber, which isequipped to circulate an aqueous buffer solution of alcohol and metalhydroxide. Air containing alkyl halide fumigant (i.e., fumigant/airmixture) is then passed through the absorber/scrubber apparatus suchthat the fumigant/air mixture and the buffer solution come into contact,causing the fumigant to be absorbed by the alcohol and thereby cleaningthe air of the fumigant. The captured alkyl halide then reacts with themetal hydroxide to yield a metal halide. A purge stream containingconcentrated metal halide solution, or metal halide slurry, iscontinuously discharged to avoid buildup of solids and contaminants inthe system. Upon discharge from the absorber/scrubber apparatus, thesolid metal halide will be precipitated and separated from the aqueousalcohol and metal hydroxide solution that remains. After the salt (e.g.,metal halide) recovery process, the solution is fed back to the absorberas absorbing solution. In an embodiment, the fumigant/air mixture isprocessed in continuous mode and the buffer solution is processed incontinuous mode but recirculating mode. In an embodiment, thefumigant/air mixture is processed in continuous mode and the buffersolution is processed in batch mode.

DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, reference ismade to the following detailed description of exemplary embodimentsconsidered in conjunction with the accompanying drawings, in which:

FIG. 1 is a schematic diagram of a process/apparatus, which can beoperated in either batch or recirculation mode for recovering andconverting an alkyl halide in accordance with the present invention;

FIG. 2 is a schematic diagram of a batch process/apparatus forrecovering and converting an alkyl halide in accordance with the presentinvention;

FIG. 3 is a schematic diagram of a recirculation process/apparatus forrecovering and converting an alkyl halide in accordance with the presentinvention;

FIG. 4 is a graph showing the results of a study on the effect ofpacking on halide absorption in the batch mode depicted in FIG. 2 ,wherein the x-axis corresponds to the time-on-stream and the y axisrepresents MeBr concentration in the liquid product, for scenarios bothwith and without packing;

FIG. 5 is a graph depicting the results of a study on the absorbingcapacity of various solvents, by plotting the MeBr concentration of theliquid product (see the y-axis) of various alcohol solvents as afunction of time (see the x-axis);

FIG. 6 is a graph illustrating the impact of the concentrations of twocommon metal hydroxides on the absorbing capacity of various solvents,by plotting the resultant MeBr concentration in the gas product (see they-axis) as a function of time (see the x-axis) for various hydroxidesand concentrations;

FIG. 7 is a graph depicting the stabilized values of MeBr removal (inpercentage) from the gas phase (see the left-hand y-axis) and the MeBrconcentration in MeBr-depleted gas (see the right-hand y-axis) for thenumbers (see the x-axis) associated with the solutions specified inTable 2 below;

FIG. 8 is a graph showing the results of a study on the effects ofgas-liquid (G-L) contact time on MeBr absorption by plotting MeBrconcentration in the gas product (see the y-axis) as a function of time(see the x-axis) for varying gas-liquid contact times, in therecirculation mode depicted in FIG. 3 ;

FIG. 9 is a graph illustrating the effect of superficial gas velocity(or residence time) on absorption in the recirculation mode depicted inFIG. 3 by plotting MeBr concentration in the gas product (see they-axis) as a function of time (see the x-axis) for multiple flow rates;

FIG. 10 is a graph showing the effect of varying gas/liquid ratios andflow rates on absorption for IOg NaOH/100 ml Ethanol solution byplotting MeBr concentration of the gas product (see the y-axis) againsttime (see the x-axis) for varying gas/liquid ratios and flow rates; and

FIG. 11 is a graph depicting the effect of varying gas/liquid ratios andflow rates on absorption for IOg KOH/100 ml ethanol solution by plottingMeBr concentration of the gas product (see the y-axis) against time (seethe x-axis) for varying gas/liquid ratios and flow rates.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

The exemplary embodiment disclosed hereinafter, which is only one ofmany exemplary embodiments of the present invention, was developed forapplication in the recovery of a substantial amount of the methylbromide used as the fumigation gas for fumigating logs of wood, followedby its conversion to a value-added product. The waste fumigation gastreated in accordance with the present invention better complies withemission regulations. Although the process and apparatus described beloware directed to the recovery and conversion of methyl bromide, it shouldbe understood by a person of ordinary skill in the art that they arealso effective for recovering and converting other alkyl halidefumigants.

In the process of the present invention, the scrubbing solution is analcohol-based buffer solution, which is not discarded, but rather isseparated from the produced suspended solid, namely metal halide, andrecycled, thereby further enhancing the economic efficiency andviability of the process. All of the reactants for the proposed processare inexpensive compared to existing processes, and metal halides, suchas sodium bromide, can be highly valuable commodity products. Anotherby-product of the process disclosed herein is methanol, a solvent thatis also recycled in the absorbing solution to aid further absorption ofthe fumigant.

The one-step highly integrated wet reactive absorption process asdeveloped herein requires reduced capital and operating cost and mildprocess conditions in comparison to currently available methods. Withintensified mass transfer characteristics, highly efficient waste gastreatment can be achieved with reduction in equipment size, which makesit viable for onsite processing. In addition, the added-value byproductfrom this process improves its cost-effectiveness, and makes thefumigant treatment close to being self-sustaining economically.

While bearing in mind the foregoing prefatory comments, reference ismade to FIG. 1 , in which apparatus 10 comprises an absorber/scrubber12, such as Model No. PPS-24 Vapor Scrubber from Vapor Tech, equipped tobring the fumigant gas and dissolved metal hydroxide into contact andthereby enabling their reaction. It should be understood that anyabsorber or scrubber apparatus known to persons having ordinary skill inthe art is suitable for use as the absorber/scrubber 12 of the apparatus10. For example, in an embodiment, the absorber could be a metalliccylindrical column or tower. In some embodiments, the column could be apacked column, while in others it could be a tray tower. Variouspackings and trays are available and known and their selection is wellwithin the knowledge of persons of ordinary skill in the art.

With continued reference to FIG. 1 , a mixed air stream 14 comprisingair and an alkyl halide, such as methyl bromide, is derived from afumigation process 16 in which an alkyl halide stream 18 has been usedto fumigate an agricultural product, such as wooden logs 20, or fruit orgrain (not shown), which has been stored in a fumigation container 22.Air 24 is pumped continuously through the fumigation container 22 toaerate the fumigated agricultural products (i.e., the logs 20), as wellas the container 22 itself. In other embodiments, the mixed air stream14 may be derived from other sources and processes besides a fumigationprocess. The mixed air stream 14 exiting the container 22 carries withit the removed alkyl halide fumigant (e.g., methyl bromide) as it entersthe absorber/scrubber 12 from the bottom. During its upward travel, themixed air stream 14 comes into contact with a counter-current flowingstream of absorbing solution 26 that is fed from the top of theabsorber/scrubber 12 and travels downwardly through theabsorber/scrubber 12. In another embodiment, the mixed air stream 14 andthe stream of absorbing solution 26 can flow through the 10absorber/scrubber in the same direction.

The stream of absorbing solution 26 is a metal hydroxide-alcohol buffersolution, which functions to enhance the external mass transfer of alkylhalide from the mixed air stream 14 to the absorbing solution, as wellas to provide a stable alkyl halide conversion media. The alkyl halide(e.g., methyl bromide) is highly soluble in the absorbing alcohol,thereby facilitating its transfer from the mixed air stream 14 to theabsorbing solution. A lean air stream 28 comprising air and a reducedamount of alkyl halide is discharged from the top of theabsorber/scrubber 12 and passes through an optional de-entrainment/demisting device 30 and an in-line alkyl halide detecting/quantification(i.e., measuring) instrument 32 before venting to the atmosphere A.

As the alkyl halide is super active to react with the metal hydroxide inthe absorbing solution, two reaction products result from a bimolecularnucleophilic substitution reaction (SN2), wherein the metal is an alkalimetal (i.e., sodium, potassium or any of the Group 1 A (1) elements ofthe periodic table). One reaction product is a product alcohol whichcorresponds to the alkyl group of the alkyl halide and which is a liquidthat is miscible with the absorbing alcohol. The other reaction productis a metal halide which corresponds to the metal of the metal hydroxideand the halide of the alkyl halide and which subsequently precipitatesas a solid. The following reaction is the general reaction which occurs:CnH₂n+IX+YOH CnH₂n+OH+YXAlkyl Metal Alcohol MetalHalide Hydroxide Halide

More particularly, where, for example, the alkyl halide is methylbromide and the metal hydroxide is sodium hydroxide, the reaction willproceed as follows to produce methanol as the product alcohol and sodiumbromide as the metal halide:CHsBR+NaOH+CHsOH+NaBrMethyl Sodium Methanol SodiumBromide Hydroxide Bromide

Referring still to FIG. 1 , stream 34, which contains metal halide andalcohols, is supplied to absorbing solution drum 36 from theabsorber/scrubber 12. A small make-up stream 38, which containsabsorbing alcohol, is also supplied to the absorbing solution drum 36 tocompensate for any absorbing alcohol that may have been lost due toreaction with the product alcohol or evaporation into the air stream orother losses. Similarly, a make-up alkali stream 40, which containsmetal hydroxide and alcohol at a certain concentration, is supplied tothe absorbing solution drum 36. A discharge stream 42 exits theabsorbing solution drum 36 via pump 44. After leaving the pump 44, thestream 42 is divided into the absorbing solution stream 26 and a purgestream 46. The purge stream 46 passes through a solid-liquid separationapparatus 48, such as a Russell Eco Separator, resulting in (i) a stream50 containing a negligible amount of dissolved salt (e.g., metalhalide), which stream 50 is returned to the absorbing solution drum 36,and (ii) collected solids 52, namely metal halide, that can be packedfor sale.

The transfer of the alkyl halide fumigant from the mixed air stream 14to the liquid absorbing solution in the absorber/scrubber 12 takes placeprimarily on the column packing or trays (not shown) of theabsorber/scrubber 12. The absorbing solution typically comprises analkali-alcohol solution and may, for example, be methanol, ethanol,butanol, isopropanol, or combinations thereof. The mass fraction of thealcohol in the absorbing solvent will vary, in general, but in someembodiments the mass fraction will be from about 0 to about 1.Accordingly, the water content (i.e., aqueous component) of theabsorbing solvent ranges from about 0 to about 1. The concentration ofmetal hydroxide in the absorbing solution will vary, in general, but insome embodiments the concentration will be from about 0 g/100 ml solventto about 50 g/100 ml of solvent. The flow rate of the absorbing solutionstream 26 as it flows into the absorber/scrubber 12 will vary dependingon, amongst other things, (i) the concentration of the fumigant in thegas stream, (ii) gas stream flow rate, (iii) the desired fumigantconcentration in the outlet gas stream, and (iv) the solubility of thefumigant in the absorbing solution.

The flow rate is determinable by persons of ordinary skill in the artand is typically determined as part of the process design. It is desiredthat the concentration of fumigant in the lean air stream 28 will befrom a trace amount (i.e., in the parts per billion range) to anundetectable amount. The temperature of the absorption column within theabsorber/scrubber 12 will be maintained at a value selected to enhancethe solubility of the fumigant in the alcohol, and also inhibitevaporation of the solvent into the gas stream. In some embodiments,this temperature will be kept at a value from about room temperature(e.g., about 20° C. to about 26° C.) to about 50° C. The operatingpressure in the absorption column will depend on the pressure of mixedair stream 14 and may be higher than atmospheric pressure. In someembodiments, the operating pressure may be at least about atmosphericpressure (e.g., 1 atmosphere, or 14.7 pounds per square inch).

The formed product alcohol will, in general, be miscible with theabsorbing solution, and the metal halide will precipitate, therebyfacilitating its separation from the product stream of the reactor. Forany absorbing solution stream, the concentration of metal hydroxideshould be controlled to meet any TSS and TDS specified by themanufacturer of the pump 44, and any associated pipe designspecification.

As mentioned, the process of the present invention may be practiced inconjunction with fumigation of agricultural products in variouscontainers or enclosures. In some embodiments, the containers may besealed shipping containers, trailers, railway cars, mills, andwarehouses. The fumigated product may be agricultural products,including wood products such as logs, as well as fruits or grains. Theconcentration of the fumigant in the mixed air stream 14 exiting thecontainer 22 during aeration will vary with time. In certainembodiments, the concentration will vary from about 0.25 g fumigant/gmixture to about 0.0 g fumigant/g mixture. The flow rate of the airstream 24 will vary depending on the alkyl halide fumigant, and the sizeof the container 22. In the fumigation of wood products in shippingcontainers, the air flow rate of the air stream 24 may be as high as1200 ft³/min at room temperature.

After the liquid level in the absorber/scrubber 12 remains unchanged forsome time, gas flow is turned on, and the measuring of time-on-streamcommences. The countercurrent flowing stream of absorbing solution 26and the gas stream to be cleaned provides large contact area and createsa relatively higher concentration difference between the two phases,which is the driving force for mass transfer.

FIG. 2 depicts a batch process and apparatus 110 for recovering andconverting an alkyl halide in accordance with the present invention.Hereinafter, this setup will be referred to as the Batch Mode Setup.Raschig rings (PTFE, L×O.D.×thickness of 3 mm×3 mm×1 mm) are packed intoan absorber 112 to a height of 6″. After such packing, 50 ml ofabsorbing/reaction solution is first transferred into the reservoir ofthe Batch Mode Setup, and the time-on-stream is measured from the timethe gas flow is turned on. A stream of MeBr-rich gas 114 flowing fromgas source 116 is regulated by a mass flow controller 118 (MFC) andpasses through check valve 120 and control valve 122 on its way to aninlet 124 of the absorber 112. The MeBr-rich gas stream 114 is suppliedto a bottom portion 126 of the packed bed, and bubbles through theflooded packed bed before exiting through outlet 128 and then passingthrough a gas chromatography setup 130 or vent 132 via valve 134.

FIG. 3 depicts a schematic diagram of apparatus 210 which can beoperated as a batch or recirculation process for recovering andconverting an alkyl halide in accordance with the present invention.Hereinafter, this setup will be referred to as the Recirculating ModeSetup. As shown in FIG. 3 , the effective flow path of theabsorber/reactor section 212 of the Recirculating Mode Setup has an IDof ¼″, a height of 21.26″ (54 cm) and is packed with 3 mm Raschig rings(PTFE, L×O.D.×thickness 3 mm×3 mm×1 mm). After such packing, 20 ml ofsolution is first transferred into the Recirculating Mode Setup and thencirculated at a selected flow rate for the absorption process. A streamof MeBr-rich gas 214 flowing from gas source 216 is regulated by massflow controller (MFC) 218 and passes through check valve 220 and controlvalve 222 on its way to an inlet 224 of the absorber 212. High-pressureliquid chromatography pump 226 drives the fluid flow. After the liquidlevel at the bottom of the absorber 212 remains unchanged for 10 min,gas flow is turned on, and the measuring of time-on-stream commences.The countercurrent flow of absorbing solution 228 and the gas stream tobe cleaned provides large contact area and creates a relatively higherconcentration difference between the two phases, which is the drivingforce for mass transfer. Gas 230 exits the absorber 212 through outlet232 and then passes through a gas chromatography setup 238 or vent 236via valve 234.

In order to describe the invention in more details, the followingexamples are set forth:

Example 1 Batch Mode Operation: Effect of Packing

The effect of packing (FIG. 4 ) on halide absorption was studied in theBatch Mode Setup using pure IPA (Isopropyl Alcohol), and the MeBrconcentration in the liquid phase was measured. The liquid phase MeBrconcentration was found to rapidly increase during the first 2 hours TOS(Time-On-Stream) for both cases, but at a much faster rate when usingpacking. With packing, the MeBr concentration approaches a stable valuestarting from the second hour and appears to reach that value,considered to be the maximum absorbing capacity of the solvent, at aboutthe third hour of the process. The packing provides large interfacialcontact area between the gas and liquid, by breaking the gas bubbles,the effect of which is the enhancement of inter-phase mass transfer.Therefore, packing materials with high specific surface area per unitvolume can be used to improve the process efficiency for the capture ofMeBr by the liquid phase.

Example 2 Batch Mode Operation: Base Solvent Screening

The data shown in FIG. 5 were collected from a set of experimentsconducted in the Batch Mode Setup. The higher the number of carbonatoms, or molecular weight, or boiling point of the solvent, the higheris its absorbing capacity. Since Butanol is much more expensive than theother three solvents, based on cost considerations, IPA will likely bethe most viable solvent.

Example 3 Batch Mode Operation: Metal Hydroxides Screening

The MeBr-rich liquid solution cannot be directly disposed of withoutincurring significant cost, effort was also made to develop a greenprocess. Therefore, the captured MeBr can either react with the metalhydroxide (YOH) by mixing the MeBr-rich liquid solution with YOH in aseparate vessel, or it can be directly reacted with YOH duringabsorption which may even enhance absorption because of the concomitantpreservation of driving force for mass transfer.

The present invention adopts the latter approach. The two most commonlyused YOH (i.e., NaOH and KOH) were used to investigate the effect of theaddition of YOH on the capture and conversion process in the Batch ModeSetup.

According to Table 1, NaOH is generally much more soluble in water thanin alcohols. Therefore, pure DI-H20, and DI-H20/alcohol mixture werefirst studied as the base solvent. For the latter mixture, because ofthe formation of two phases, an aqueous phase that contains almost allthe NaOH, and the alcohol phase that contains little NaOH, this solventsystem exhibited much lower absorbing capacity than the alcohol-basedsystems, as shown in FIG. 6 .

Table 1: Solubility of YOH in different solvents

NaOH (g/100 ml solvent) KOH (g/100 ml solvent)

Water 111 112

Methanol 23.8 43.4

Ethanol «13.9 40 or 30.5

IPA 11

The results for all the solutions tested are presented in FIG. 6 , andwere obtained from the Batch Mode Setup. For alcohol-based solutions,the increase of YOH concentration can greatly enhance the absorbingcapacity. The results also reveal that the KOH is more active than NaOH,and ethanol appears to be the best solvent among all studied solventswhen YOH is added.

The stabilized values of % removal of MeBr from gas phase and the MeBrconcentration in the MeBr-depleted gas using different absorbingsolutions were corrected to account for the effect of solvent vaporpressure, and the results summarized in FIG. 7 and Table 2. The mosteffective absorbing solution is 20 g KOH/100 ml Ethanol.

Table 2: Solvent ID reference

MeBr Removal % MeBr_GC %

Solvent ID Solution composition in Gas Phase:

-   -   1 1.5 g NaOH+50 ml Water 12.67% 3.69%    -   2 250 ml IP A 13.35% 3.59%    -   3 3 g NaOH+45 ml IPA+5 ml H2O 18.15% 3.43%    -   4 50 ml MeOH 11.06% 3.35%    -   5 16 g NaOH+38 ml Water+12 ml Ethanol 30.76% 2.95%    -   6 1.5 g NaOH+50 ml Ethanol 63.85% 1.51%    -   7 2.5 g NaOH+50 ml Ethanol 64.64% 1.48%    -   8 5 g NaOH+50 ml MeOH 63.65% 1.42%    -   9 10 g NaOH+50 ml MeOH 69.18% 1.22%    -   10 5 g NaOH+50 ml Ethanol 74.64% 1.07%    -   11 5 g KOH+50 ml IPA 79.24% 0.89%    -   12 5 g KOH+50 ml Ethanol 79.62% 0.86%    -   13 10 g KOH+50 ml Ethanol 86.12% 0.59%

Example 4 Recirculating Mode Operation: Formation of Suspended Solids

The major challenges for the recirculation test were from theprecipitation of solids due to (i) the formation of lower solubilityproducts (from the reaction of YOH and MeBr) as well as (ii) the loss ofalcohol solvents at high gas flow rates when no make-up alcohol solutionwas added to the system. Tests with IOg and 20g KOH/100 ml Ethanol at 5ml/min recirculation rate and 40 seem air flow rate (without MeBr)revealed that there was no KOH or NaOH in the precipitates whichindicates that the precipitates are the products from the reaction ofthe YOH with MeBr.

Example 5 Recirculating Mode Operation: Effect of Gas-Liquid (G-L)Contact Time

The effect of G-L contact time in the Recirculating Mode Setup wasexperimentally studied by keeping the absorbing solution in batch mode.The results are summarized in FIG. 8 . It should be noted that, althoughthere was a lag in the measurement of the 20 seem and 30 seemexperiments, since the solution concentration was far in excess andapproximately constant, the decrease of solution volume in the absorberwas negligible (as there was solution above the packing, and the packingwas always immersed in the solution), the gas composition at the topsurface of the solution can remain constant during the 3 -hour durationof the experiment. Therefore, the data reported in the second plot forthe 20 seem and 30 seem results can be considered the real performancedata.

As expected, the decrease in gas flow rate can effectively decrease theamount of MeBr in the gas exit stream, and the best result was 0.3 mol %at 20 seem. Compared with the set of experiments conducted in the BatchMode Setup (depicted in FIG. 2 ), where the exit gas composition was inthe range of 1.05-1.07 mol %, the MeBr composition reduced to 0.67-0.7mol % at 40 seem. This reduction can be attributed to the reduced ID andincreased length of the absorber.

Example 6 Recirculating Mode Operation: NaOH/H₂O Solution as ModelSolvent

In order to study the performance of the process with the absorbingsolution in recirculation mode while avoiding the pump blockage problem,20 g NaOH/100 ml H2O solution was used.

As shown in FIG. 9 , at 40 seem MeBr/Air flow rate, liquid (20 gNaOH/100 ml H2O) flow rate was increased from 3.5 ml/min to 10 ml/min.The results show that the 5 ml/min liquid flow rate is sufficient forachieving complete wetness of the absorber packing in the recirculationmode. At 10 ml/min, the gas flow rate was reduced to 20 seem. Asexpected, the MeBr mol % in gas phase was reduced compared to that at 40seem. The experiment was also run at 20 seem with 35 ml solution but innon-recirculating (batch) mode. Compared with the 20 sccm/10 ml/min run,it seems the mixing due to the recirculation of liquid phase can becompensated for by the gas flow. For the comparison of batch mode andrecirculation mode, based on the water recirculation results, thereappears to be no difference for batch mode and recirculating mode at aliquid flow rate of 10 ml/min, although more experimental runs will beneeded to confirm this observation. Also, although this may not beapplicable for the YOH/Ethanol system, it should be noted that therecirculation mode requires only 20 ml (or even less) of solution, whilethe batch mode requires 35 ml solution, for capturing and convertingsimilar amounts of MeBr. Furthermore, for practical operation, it isbetter to run in recirculation mode, which will enable the streamexiting the slurry reservoir to be passed into a precipitator forremoval of the solid (salt) product, and add a make-up ethanol (orsolvent) stream to the process stream after it exits the precipitator.The 20 sccm/35 ml result of 3.78 mol % is worse than that from the 40sccm/50 ml (3 g NaOH/100 ml H2O) result of 3.69 mol % (FIG. 2 Batch ModeSetup), even with the NaOH concentration increased to 20 g NaOH/100 mlH2O. The main reason is that the superficial residence time in theRecirculating Mode Setup (FIG. 3 ) is 1/3.2 that of the Batch Mode Setup(FIG. 2 ).

Example 7 Recirculating Mode Operation: YOH/Alcohol Solution

The YOH/alcohol solution cannot be successfully processed inrecirculating mode for 3 hours due to the formation of precipitateswhich clog the pump. For the IOg NaOH/100 ml Ethanol solution,experiments were run (FIG. 10 ) at different gas/liquid ratios whilefixing the gas flow rate at 50 seem. As expected, the MeBr concentrationin the exit gas stream decreases with the increase of L/G ratio, due toa higher coverage of the cross-section of the packing bed and increasedliquid residence time.

In addition to the data presented in FIG. 11 , 20 g KOH/100 ml Ethanolat flow rates of 5 ml/min and 10 ml/min was also tested, but theexperiment had to be suspended because the pump pressure was too high(>1600 psi) even after only 5 minutes of recirculation. The liquid flowrate was fixed at 5 ml/min based on the previous experimental resultsusing water. When the liquid flow rate was set to 10 ml/min, the pumppressure rose to a value >1600 psi very quickly. The observations shownin FIG. 11 confirm the previous conclusion that higher YOH concentrationenhances the MeBr capture, and ethanol exhibits better performance thanIPA.

It will be understood that the embodiments described herein are merelyexemplary and that a person of ordinary skill in the art may make manyvariations and modifications without departing from the spirit and scopeof the invention. All such variations and modifications are intended tobe included within the scope of the invention as defined in thefollowing claims.

What is claimed is:
 1. A process for capturing and converting fumigantsusing an absorber/scrubber apparatus, said process comprising the stepsof: a) feeding an alcohol and metal hydroxide buffer solution into saidabsorber/scrubber apparatus; b) continuously feeding an alkyl halidefumigant/air mixture into said absorber/scrubber apparatus such thatsaid alkyl halide fumigant/air mixture contacts said alcohol and metalhydroxide buffer solution, wherein at least a portion of a fumigantcomponent of said alkyl halide fumigant/air mixture transfers from saidalkyl halide fumigant/air mixture to said alcohol and metal hydroxidebuffer solution to thereby create a reaction by which, said fumigantcomponent reacts with a metal hydroxide component of said alcohol andmetal hydroxide buffer solution to yield a second mixture comprisingproduct alcohol, unreacted metal hydroxide, and a metal halide; c)feeding said second mixture from said absorber/scrubber apparatus to anabsorbing drum and combining it with a small make-up stream, whichcontains absorbing alcohol, and a make-up alkali stream, which containsmetal hydroxide and alcohol at a certain concentration, to form adischarge stream; d) dividing said discharge stream into a purge stream,comprising said unreacted metal hydroxide, said product alcohol and saidmetal halide, and an absorbing solution stream; e) separating said metalhalide from said purge stream to yield solid metal halide, wherein saiddividing and separating steps are performed continuously and inconjunction with steps a)-c); and f) recirculating said absorbingsolution stream into said absorber/scrubber apparatus, wherein saidabsorbing solution stream is used as said alcohol and metal hydroxidebuffer solution during the repetition of step a).
 2. The process ofclaim 1, further comprising the step of discharging a treated lean airstream to post-processing equipment and measuring instrument foremission to atmosphere.
 3. The process of claim 1, wherein said alcoholcomponent of said alcohol and metal hydroxide buffer solution includestwo alcohols.
 4. The process of claim 1, wherein said alkyl halide ismethyl bromide.
 5. The process of claim 1, wherein said alkyl halidefumigant/air mixture is fed into said absorber/scrubber apparatus in afirst direction and said alcohol and metal hydroxide buffer solution isfed into said absorber/scrubber apparatus in a second direction, whichis opposite said first direction.
 6. The process of claim 1, whereinsaid alcohol component of said alcohol and metal hydroxide buffersolution comprises an aqueous alcohol.
 7. The process of claim 1,wherein said alkyl halide fumigant/air mixture is fed into saidabsorber/scrubber apparatus in a first direction and said alcohol andmetal hydroxide buffer solution is fed into said absorber/scrubberapparatus in a second direction, which is the same as said firstdirection.
 8. The process of claim 1, wherein said metal hydroxidecomponent of said alcohol and metal hydroxide buffer solution comprisessodium hydroxide.
 9. The process of claim 1, wherein said metalhydroxide component of said alcohol and metal hydroxide buffer solutioncomprises potassium hydroxide.
 10. The process of claim 1, wherein saidalcohol component of said alcohol and metal hydroxide buffer solutioncomprises an alcohol selected from the group consisting of methanol,ethanol, butanol and isopropanol.
 11. The process of claim 1, whereinsaid absorber/scrubber apparatus includes a liquid absorbing solution,said liquid absorbing solution comprising an aqueous alcohol and a metalhydroxide, said metal hydroxide being the same as said metal hydroxidecomponent of said alcohol and metal hydroxide buffer solution.
 12. Theprocess of claim 1, wherein said absorber/scrubber apparatus includes aliquid absorbing solution, said liquid absorbing solution comprising anaqueous alcohol and a metal hydroxide, said aqueous alcohol being thesame as said alcohol component of said alcohol and metal hydroxidebuffer solution.
 13. The process of claim 1, wherein said fumigantcomponent of said alkyl halide fumigant/air mixture is derived from aprocess other than a fumigation process.
 14. The process of claim 1,wherein said alcohol and metal hydroxide buffer solution has an alcoholcomponent with a mass fraction of greater than 0 up to about
 1. 15. Theprocess of claim 1, wherein said alcohol and metal hydroxide buffersolution has an aqueous component with a mass fraction of from about 0to about
 1. 16. The process of claim 1, wherein said metal hydroxidecomponent of said alcohol and metal hydroxide buffer solution has aconcentration in a range of greater than 0 g/100 ml of said alcohol andmetal hydroxide buffer solution up to about 50 g/100 ml of said alcoholand metal hydroxide buffer solution.
 17. The process of claim 1, whereinsaid fumigant component has a concentration in a range of greater than 0g fumigant/g fumigant/air mixture up to about 0.25 g fumigant/g offumigant/air mixture.
 18. The process of claim 1, further comprising thesteps of obtaining a lean air stream from said absorber/scrubberapparatus and releasing said lean air stream to atmosphere, wherein nofurther treatment steps are performed on said lean air stream prior tosaid releasing step.
 19. Apparatus for capturing and convertingfumigants, comprising: first feeding means configured and arranged forfeeding a buffer solution into an absorber/scrubber; second feedingmeans configured and arranged for continuously feeding an alkyl halidefumigant/air mixture into said absorber/scrubber such that said alkylhalide fumigant/air mixture contacts said alcohol and metal hydroxidebuffer solution, wherein at least a portion of said fumigant componentof said alkyl halide fumigant/air mixture transfers from said alkylhalide fumigant/air mixture to said alcohol and metal hydroxide buffersolution to thereby create a reaction by which said fumigant componentreacts with said metal hydroxide component of said alcohol and metalhydroxide buffer solution to yield a second mixture comprising productalcohol, unreacted metal hydroxide, and a metal halide; an absorbingdrum configured for feeding said second mixture from saidabsorber/scrubber to said absorbing drum and combining it with a smallmake-up stream, which contains absorbing alcohol, and a make-up alkalistream, which contains metal hydroxide and alcohol at a certainconcentration, to form a discharge stream; dividing means configured andarranged to divide said discharge stream into an absorbing solutionstream and a purge stream, which comprises said unreacted metalhydroxide, said product alcohol and said metal halide; return meansconfigured and arranged to return said absorbing solution stream intosaid absorber/scrubber; and separating means configured and arranged forcontinuously separating said metal halide from said purge stream toyield solid metal halide.
 20. The apparatus of claim 19, furthercomprising post-processing treatment means configured and arranged fortreating a lean air stream discharged from said absorber/scrubber priorto its venting to atmosphere, said post-processing treatment meansincluding measuring means for measuring any fumigant contained in saidlean air stream.
 21. The apparatus of claim 19, wherein saidabsorber/scrubber comprises a metallic cylindrical column.
 22. Theapparatus of claim 19, wherein said absorber/scrubber comprises a traytower.
 23. The apparatus of claim 19, wherein said absorber/scrubbercomprises a packed column.
 24. The apparatus of claim 19, wherein saidabsorber/scrubber is configured and arranged to be kept at a temperatureof from about 20° C. to about 50° C.
 25. The apparatus of claim 19,wherein said absorber/scrubber is configured and arranged to be kept atan operating pressure of at least about one atmosphere.